芳烃蒸汽催化重整制氢研究进展

doi:10.16085/j.issn.1000-6613.2021-0452

摘要/Abstract

摘要：

氢能是一种清洁的二次能源，具有绿色环保、零污染、零碳排放等优点。芳烃蒸汽重整制氢原料来源广、单位体积原料产氢量高，在重油焦油清除升级、便携式移动制氢等领域极具应用价值，其核心在于高性能催化剂的开发。文章首先从芳烃重整反应特性、反应网络、动力学模型构建和吸附解离等方面对其反应动力学及机理进行了概述，认为采用热力学理论计算、先进的原位表征技术和严密的逻辑论证实验等综合手段是加深反应动力学和机理认知的关键；其次，按照催化剂组成分类，评述了不同活性组分、载体及助剂的特点，基于镍基双金属活性组分的协同效应、钙钛矿载体的强储/释氧能力和碱性助剂的酸调控作用，指出碱性助剂改性的负载型镍基双金属钙钛矿催化剂是其发展方向。

关键词: 芳烃, 重整, 制氢, 催化剂, 反应动力学及机理

Abstract:

Hydrogen energy as a kind of clean energy has the advantages of environmental friendly, zero pollution and zero carbon emission. The steam reforming of aromatics with vast raw materials has a high hydrogen production per unit volume and shows great application value in tar removal and upgrading, portable hydrogen production, etc. The core of aromatics steam reforming is the development of high performance catalysts. Firstly, the progresses of aromatics reforming kinetics and mechanism were summarized mainly from the aspects of reaction characteristics, reaction network, kinetic model construction, adsorption and dissociation. It was considered that the key to deepening the understanding of kinetic process and mechanism was the integration of thermodynamic theoretical calculations, advanced in-situ characterization technologies and rigorous logical demonstration experiments. Then, various active components, supports and promoters of catalysts for aromatics steam reforming were reviewed according to the classification of supported catalysts components. Based on the nickel-based bimetallic synergy, strong oxygen storage-release capacity of perovskite supporters and acidity regulation of alkaline additives, the development of nickel-based bimetallic supported perovskite catalysts promoted by the alkaline additives was proposed.

Key words: aromatic hydrocarbon, reforming, hydrogen production, catalyst, reaction dynamics and mechanism

中图分类号:

TQ116.2

刘嘉辉, 孙道安, 杜咏梅, 李春迎, 刘昭铁, 吕剑. 芳烃蒸汽催化重整制氢研究进展[J]. 化工进展, 2021, 40(9): 4782-4790.

LIU Jiahui, SUN Dao’an, DU Yongmei, LI Chunying, LIU Zhaotie, LYU Jian. Progress on hydrogen production from catalytic steam reforming of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4782-4790.

图/表 4

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反应物	密度（20℃）/g·cm^－3	理论产氢量/mmol·mL^－1
乙酸	1.050	70.0
二甲醚	0.666	86.7
乙醇	0.789	102.8
正十二烷	0.750	162.9
苯	0.880	169.0
甲苯	0.866	169.2
萘	1.145	214.4

反应物	密度（20℃）/g·cm^－3	理论产氢量/mmol·mL^－1
乙酸	1.050	70.0
二甲醚	0.666	86.7
乙醇	0.789	102.8
正十二烷	0.750	162.9
苯	0.880	169.0
甲苯	0.866	169.2
萘	1.145	214.4

制氢方式	实验室实际产氢量/kg H₂·(kg 原料)^－1	制氢成本/CNY·kg^－1
甲烷重整	0.313	14^①
甲苯重整^②	0.196	20~25^③
碱式电解水	—	40

制氢方式	实验室实际产氢量/kg H₂·(kg 原料)^－1	制氢成本/CNY·kg^－1
甲烷重整	0.313	14^①
甲苯重整^②	0.196	20~25^③
碱式电解水	—	40

反应物	催化剂	反应条件^①	积炭量^②	芳烃转化率/%	H₂收率^③/%	文献
苯	NiO/泡沫陶瓷	750℃，WHSV=5.6h^-1，S/C=2.0	—	85.5	59	［6］
甲苯	Ni/CGA-1d	800℃，WHSV=2.6h^-1，S/C=2.0	0.034g_coke·h·g_cat^－1	91.5	58.2	［7］
甲苯	Ni/MgO-Al₂O₃	650~800℃，WHSV=5.2h^-1，S/C=1.7	2.55~4.86mg·(g C_feed)^－1	95.4	69	［8］
甲苯	Ni/La_0.7Sr_0.3AlO_3-_δ	600℃，WHSV=1.84h^-1，S/C=2.0	9.3mg·g_cat^－1	53.0	49.9	［9］
甲苯	Ni-K/La_0.7Sr_0.3AlO_3-_δ	650℃，WHSV=3.73h^-1，S/C=2.0	7.3mg·g_cat^－1	100	79	［10］
甲苯	Ni-Fe/zeolite	800℃，WHSV=1.0~2.3h^-1，S/C=2.0	—	74	65	［11］
萘	Ni/Ce_0.75Zr_0.25-_xMn_xO₂	700℃，GHSV=20000h^-1，S/C=2.0	(1.1±0.3)mg·g_cat^－1	100（120min）	—	［12］